Stable nitromethane composition



United States Patent 3,2$8,867 STABLE NITRGMETHANE CGMPOSITION RichardS. Egly, West Terre Haute, and Quentin R.

.leftries, Torre Hante, Ind, assignors to Commercial SolventsCorporation, New York, N.Y., a corporation of Maryland No Drawing. FiledFeb. 17, 1965, Ser. No. 433,519 Claims. (Cl. 260-644) confined in aheavy-walled vessel which Will Withstand the development of considerableinternal pressure. An embargo is presently in existence on shipment ofnitromethane in bulk containers by both the manufacturer and theInterstate Commerce Commission. The ordinary drum meeting ICCSpecification 17E ruptures at low pressures and nitromethane isregularly shipped in this container with a layer of nitrogen in the headspace to replace the air. This method of transportation, however, hasresulted in financial hardship for the user and has in generalrestricted the use of nitromethane in many applications where it wouldbe of considerable technical value.

It is an object of this invention to provide stable com ositions ofnitromethane. It is another object of this invention to providecompositions of nitromethane having improved stability for bulktransportation. Another object is to provide a method of bulktransportation of nitromethane.

It has been discovered that a combination of nitromethane and a specificminimum amount of a stabilizing liquid selected from the groupconsisting of acetone, toluene, benzene, 1,2-butylene oxide,cyclohexanone, 1,4- dioxane, l-nitropropane, methanol Z-nitropropane,methylene chloride, methyl chloroform, and nitroethane are stable toextreme shock and provide a safe method for bulk transportation ofnitromethane.

More particularly the liquid combinations of this invention have thefollowing compositions:

Combinations containing at least the minimum volume of stabilizer arenot detonated when confined in a heavywalled vessel and subjected tosevere shock. A special test which will subsequently be described indetail has been devised to measure the degree of stability of chemicalswhich do not detonate in any of the tests previously used.

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The combinations of this invention provide a variation of properties sothat a particular combination usually can be used directly withoutseparation into the components. However, if separation is desirable,means for so doing can be readily devised by those skilled in the art.

The common tests employed to determine Whether or not a substance shouldbe placed in the explosive category do not yield useful information onnon-explosives. Many substances will exhibit energy release whensubjected to sources of high energy such as the shock wave of adetonated high explosive, heat, a combination of heat and shock atambient pressure, a combination of heat and shock'at elevated pressure,or adiabatic compression.

The new test has been devised to measure the amount of energy releasedwhen a material which cannot be detonated is subjected to severe shockInto a solid cylinder of cold rolled steel having a diameter of 5 inchesand a length of 6 inches, is drilled a hole 1 inch in diameter and 4inches in depth having the same axis as the cylinder. The face of thecylinder is grooved by a single radial cut Ms inch wide and inch deep.In use, the opening of the hole is covered with a 5 lb. test weight cutfrom .a cylindrical steel rod having a diameter of approximately 2%inches. It length will be about 3 inches.

To conduct the test, the cylinder is placed on an unyielding support atthe foot of a perpendicular measuring board 20 ft. high marked in 1 it.increments. A liquid sample size of 4 milliliters is delivered to a testtube 13 x 100 mm. and placed in the hole bored in the cylinder. A No. 8electric dynamite cap is placed in the test tube with sample and thelead wires are placed in the groove cut in the face of the cylinder. Thetest weight is centered over the hole, the cap is fired, and the heightto which the weight is flung by the energy released is observedvisually. Five determinations are made for each test substance. Data aregiven in Table 1 showing the results obtained on a number of commercialmaterials.

TABLE 1 Chemical Quantity, ml. Height, ft.

Nitromcthane 4. O 48 Hydrogen peroxide, 4. 0 39 Hydrazine 4. 0 39Ethylene oxide... 4. (l 10 1.3-butadiene 4. (J 4 4. O 5 Bntylene oxide4. 0 5 Cyclohexanone 4. O 4 Dioxane 4. (l 5 l'nitropropane 4. (l 82-nitropropane 4. 0 7 Methanol 4. 0 5 Methylene chloride 4. 0 l2 Methylchloroform 4. 0 6 Nitroethaneun. 4. 0 11 Acetone 4. 0 6

Hydrogen peroxide 90% and hydrazine released sufficient energy in thistest to hurl the weight to a height of 39 feet yet they are shippedregularly in tank cars and tank trucks without special regulation. T-hisbasis of experience is the support for the definition of stabilizednitromethane as that combination which releases no more energy in thespecial test described than does 90% hydrogen peroxide or hydrazine.However, as an added safety measure for transportation purposes the rulehas been adopted that stable nitromethane combinations safe for shipmentin bulk are those that yield an average test height no greater than 13feet when tested as described.

The practice of this invention is further illustrated by the followingexamples:

Example 1 Commercial grade toluene 21 g. and nitromethane 79 g. weremixed. A 4 ml. sample was tested according to the described method. Theweight was flung to an average height of 13 feet in five trials and thecombination was adjudged stable for bulk transportation.

Examples 2-12 In a manner similar to Example 1, other combinations ofnitromethane and stabilizing amounts of a second component were tested.The weights were flung to an average height of no more than 13 feet andthe combinations were adjudged safe for shipment.

COMPOSITION OF C OMBINATTONS Having described this invention, what isclaimed is: 1. In combination, a liquid composition having improvedstability to detonation by shock comprising liquid nitromethane .and astabilizing amount of a stabilizing liquid, said stabilizing amount andsaid stabilizing liquid being:

(a) toluene in a stabilizing amount of not less than 21% by Weight,

(b) benzene in a stabilizing amount of not less than 24% by Weight,

(c) acetone in .a stabilizing amount of not less than 24% by weight,

(d) cyclohexanone in a stabilizing amount of not less than 23% byweight,

(e) l-nitropropane in a stabilizing amount of not less than 31% byweight,

(f) 2-nitropropane in a stabilizing amount of not less than 45% byweight, g) methylene chloride in a stabilizing amount of not less than42% by weight, or

(h) methyl chloroform in a stabilizing amount of not less than 50% byweight.

2. The composition of claim 1 wherein the stabilizing liquid is toluenein a stabilizing amount of not less than 21% by weight.

3. The composition of claim 1 wherein the stabilizing liquid is benZenein a stabilizing amount of not less than 24% by Weight.

4. The composition of claim 1 wherein the stabilizing liquid is acetonein a stabilizing amount of not less than 24% by weight.

5. The composition of claim 1 wherein the stabilizing liquid iscyclohexanone in a stabilizing amount of not less than 23% by weight.

6. The composition of claim 1 wherein the stabilizing liquid isl-nitropropane in a stabilizing amount of not less 0 than 31% by weight.

7. The composition of claim 1 wherein the stabilizing liquid is2-nitropropane in a stabilizing amount of not less than 45% by weight.

8. The composition of claim 1 wherein the stabilizing liquid ismethylene chloride in a stabilizing amount of not less than 42% byweight.

9. The composition of claim 1 wherein the stabilizing liquid is methylchloroform in a stabilizing amount of not less than 50% by weight.

10. A method for the stabilization of bulk quantities of liquidnitromethane to detonation by shock comprising adding to the liquidnitromethane a stabilizing amount of a stabilizing liquid, saidstabilizing amount and said stabilizing liquid being:

(a) toluene in a stabilizing amount of not less than 21% by weight,

(b) benzene in a stabilizing amount of not less than 24% by weight,

(c) acetone in a stabilizing amount of not less than 24% by weight,

(d) cyclohexanone in a stabilizing amount of not less than 23% byweight,

(e) l-nitropropane in a stabilizing amount of not less than 31% byweight,

(f) Z-nitropropane in a stabilizing amount of not less than 45 byweight,

(g) methylene chloride in a stabilizing amount of not less than 42% byweight, or

(h) methyl chloroform in a stabilizing amount of not less than 50% byweight.

References Cited by the Examiner UNITED STATES PATENTS 2,433,943 1/1948Zwicky et al. L

2,673,793 4/1954 Brodhacker l49--9O 2,809,884 10/1957 Ratje 260-6443,043,099 7/ 1962 Wilson 14989 X OTHER REFERENCES Bottomley et al.,Australian J. Chem., vol. 16, pp. 16 (1963). V

BENJAMIN R. PADGE'IT, Primary Examiner.

CARL D. QUARFORTH, LEON D. ROSDOL,

Examiners.

A, SEBASTIAN, Assistant Examiner.

1. IN COMBINATION, A LIQUID COMPOSITION HAVING IMPROVED STABILITY TODETONATION BY SHOCK COMPRISING LIQUID NITROMETHANE AND A STABILIZINGAMOUNT OF A STABILIZING LIQUID, SAID STABILIZING AMOUNT AND SAIDSTABILIZING LIQUID BEING: (A) TOLUNE IN A STABILIZING AMOUNT OF NOT LESSTHAN 21% BY WEIGHT, (B) BENZENE IN A STABILIZING AMOUNT OF NOT LESS THAN24% BY WEIGHT, (C) ACETONE IN A STABILIZING AMOUNT OF NOT LESS THAN 24%BY WEIGHT, (D) CYCLOHEXANONE IN A STABILIZING AMOUNT OF NOT LESS THAN23% BY WEIGHT, (E) 1-NITROPROPANE IN A STABILIZING AMOUNT OF NOT LESSTHAN 31% BY WEIGHT, (F) 2-NITROPROPANE IN A STABILIZING AMOUNT OF NOTLESS THAN 45% BY WEIGHT, (G) METHYLENE CHLORIDE IN A STABILIZING AMOUNTOF NOT LESS THAN 42% BY WEIGHT, OR (H) METHYL CHLOROFORM IN ASTABILIZING AMOUNT OF NOT LESS THAN 50% BY WEIGHT.